Asbestos-phosphoric acid molding composition



p 4, 1968 V.ABOLINS ETAL 3,403,033

ASBESTOSPHOSPHORIC ACID MOLDING COMPOSITION Filed Jan. 12, 1966 INVENTORS VISVALDIS ABOLINS ROBERT PLLUK THEIR AITORNEYS United States Patent 3,403,038 ASBESTOS-PHOSPHORIC ACID MOLDING COMPOSITION Visvaldis Abolins, Pittsfield, Mass., and Robert M. Lukes,

Louisville, Ky., assignors to General Electric Company, a corporation of New York Filed Jan. 12, 1966, Ser. No. 520,259 2 Claims. (Cl. 106-63) ABSTRACT OF THE DISCLOSURE Preparation of a thermosetting molding composition by first gently mixing phosphoric acid with diatomaceous earth material to provide a dry, free-flowing acid containing powder, and then gently dry blending this powder with asbestos fibers.

This invention relates to an asbestos-phosphoric acid molding composition and more particularly to a molding composition of this type having a very greatly extended working life at room temperature.

Molding compositions comprising chrysotile asbestos fibers and orthoph-osphoric acid of greater than 60% concentration are taught in US. Patent 2,336,485, Brink et al. Molded articles produced from asbestos-phosphoric acid molding compositions, such as those taught by Brink et al., are mechanically strong, hard, dense and rigid. These compositions have been used extensively for the hot-molding of arc chutes for air circuit breakers and other high temperature applications.

Among the advantages of asbestos-phosphoric acid molding material are that shrinkage of the material during the hot-molding process is minimized and that the surface of these moldings, while they may be readily machined, have a good finish obviating any need for a further finishing or polishing operation.

The spontaneous and highly exothermic reaction, which occurs when asbestos and phosphoric acid are mixed, is a well-known drawback to the prior art asbestos-phosphoric acid molding compositions and for all practical purposes, these compositions must be extensively cooled during mixing and storing to delay this spontaneous reaction. In the past this has been accomplished by mixing in the presence of Dry Ice or in a Water-cooled mixing apparatus. For example, in a typical prior art mixture, three pounds of Dry Ice were used for every three pounds of asbestos in the mixture. In addition, in order to extend the life of the composition, refrigeration Was required after mixing. In the absence of some cooling means, these compositions must be molded within a matter of minutes after mixing.

One object of the present invention is to provide an asbestos-phosphoric acid molding composition having an extended storage life at room temperature.

Another object of this invention is to provide an asbestos-phosphoric acid molding composition which need not be extensively cooled prior to being molded.

A further object of this invention is to provide a stable asbestos-phosphoric acid molding composition from which are chutes for air circuit breakers and products especially useful for other high temperature applications may be molded.

Briefly stated, in accordance with one aspect of this inventiona new and improved molding composition having a very greatly extended working life at room temperature is provided. The composition comprises a dry free-flowing mixture of phosphoric acid and a solid absorbent material which absorbent material is unreactive with phosphoric acid at room temperature. Asbestos fibers are thereafter dry blended with the dry phosphoric acid-absorbent mix- 3,403,038 Patented Sept. 24, 1968 ture. The resulting dry molding composition is essentially unreactive at room temperature yet may be readily molded to form mechanically strong, hard, dense, rigid thermoset products especially useful for high temperature applications or environments.

Although silaceous materials, similar to diatomaceous earth materials, have been used as fillers in molding compositions in the past, the fact that a composition of the asbestos-phosphoric acid type, may be rendered nonreactive by first mixing one of the components with a solid absorbent material, such as a diatomaceous earth material, has not been suggested in the prior art and was completely unexpected.

While the specification concludes with claims particularly pointing out and distinctly claiming the subject matter of the present invention, the invention may be better understood by reference to the following detailed description and the attached illustration in which:

FIGURE 1 is a photomicrograph of the crystalline structure of a molded article made from a prior art molding composition, and

FIGURE 2 is a photomicrograph of the crystalline structure of a molded article made from the molding compositions of the present invention.

In preparing the new and improved molding composition of this invention we first mix a phosphoric acid solution with a solid absorbent material to provide a dry, freefiowing acid-containing powder. For purposes of this invention the solid absorbent material must be chemically unreactive with phosphoric acid at room temperature as well as being capable of retaining the physical characteristics of a dry, free-flowing powder when admixed with at least 50 weight percent of phosphoric acid.

To the dry, free-flowing phosphoric acid-containing powder so provided we then dry blend asbestos fibers, preferably chrysotile asbestos fibers, to provide the molding composition of this invention. Wholly unexpectedly, the molding composition so provided is found to be essentially unreactive at room temperature yet readily moldable to provide a desired thermoset product. Conveniently, the product may be molded employing both heat and pressure although satisfactory products have been produced employing pressure alone with the phosphoric acidasbestos reaction going to completion at room temperature.

Preferably, the solid absorbent material is a diatomaceous earth material. Diatomaceous earth, also known as infusorial earth, is a well known silaceous material composed of the skeletal remains of small aquatic plants called diatoms. Although satisfactory dry, free-flowing acid-containing powders may be obtained from a mixture of phosphoric acid and such natural or untreated diatomaceous earth material, improved results are attained by the use of diatomaceous earth which has been suitably treated or processed such as, for example, by being calcined or subjected to a hydrothermal reaction to produce synthetic silicates. The term diatomaceous earth, therefore, is used herein in a broad sense and is intended to include the so called natural, calcined or otherwise treated or processed diatomaceous earth materials. For example, especially satisfactory results have been obtained with the processed or so called synthetic silicates of a type which are produced by the hydrothermal reaction of diatomaceous earth with an alkaline earth metal hydroxide. Synthetic calcium and magnesium silicates of this type are sold commercially by the Johns- Manville Company under the trademarks Micro-Cell and Celkate respectively; natural and calcined diatomaceous earth being sold under the trademark Celite. Especially satisfactory results have been obtained with one of the foregoing synthetic calcium silicates produced by the hydrothermal reaction of diatomaceous earth with lime and designated Micro-Cel-E. This particular material was found to absorb a concentrated phosphoric acid solution (75% acid-water solution) to the extent of four times the weight of the absorbent material and still retain the physi- 4 was continued for 5 to minutes after the mixing was completed to bring the temperature of the mix to room temperature. The resultant mixture was a dry powder, light brown in color. Two hundred and thirty-three grams cal characteristics of a dry, free-flowing powder which 5 of this mixture was mixed with 300 grams of mixed long was essentially chemically unreactive at room temperaand shoft fiber chrysotile asbestos. These components ture with the asbestos fibers dry blended therewith. were blended for three minutes in a mixer operating at Chrysotile asbestos is preferred and a mixture of short slow speed. A dry, soft, light sand-colored molding comand long fiber crylsotile asbestos is commonly used. The position was attained. Two hundred and forty grams of proportion of asbestos to phosphoric acid is not critical, 10 this composition was placed in a cavity of a compression although asbestos-phosphoric acid molding compositions type mold for an arc chute side. The mold was preheated usually comprise about 1 to 3 parts by weight of asbestos to approximately 145 C. and the mold was closed, with per part phosphoric acid. the application of a 30-ton force. The heat and pressure The exact nature of the mechanism involved in the were applied for minutes and when removed from the present invention is not entirely understood and may be 15 mold the resulting arc chute side was hard, well-filled and one of absorption or adsorption, or a combination thereof. uniform.

To simplify the description of the invention, therefore, As another example of the molding composition of the the terms absorption and solid absorbent material present invention 727.2 grams of a 75% aqueous phoshave been employed with the intention that they be given P C id Solution Was lended with 181.8 grams of an interpretation consistent with the actual mechanism or Miero-Cel-E. A laboratory blend having Some Of the combination of mechanisms involved in any given comblades removed, was used to minimize shearing action on position the mixture. Other precautions were taken to avoid heat In mixing the asbestos win th dry mixture f phosbuildup during the mixing process. The absorbed phosphoric acid and solid absorbent and also in blending the Pherie acid Was then combined With 1091 grains of P phosphoric acid solution with the solid absorbent mate- :5 mixed long and Short iiher ehfysoiiie asbestos. After m X- rial, severe agitation should be avoided since the structure g these maiefiais for 10 minutes, Several articles W of the absorbent material seems to break down under exmolded using a Steam-heated 504011 hydraulic Press to cessive stress. The tendency of the structure of the solid Produce molded ariieies having y desirable qualitiesabsorbent to breakdown may be aggravated by the slightly Moldings Produced from the Same Composition that had exothermic reaction by which the acid is absorbed or been Stored for 2 and 4 hours at room temperature, otherwise contained in the solid absorbent material. These SPeeiiVeiy, Were ieund to he Similar to those that had n materials should therefore not be blended too rapidly and InOided immediately after the Compound had been IniXedpreferably the phosphoric acid is added in small quanti- Ariieies molded from the foregoing composition in an ties to the solid absorbent material while the mixture heated mom with increased Pressure Were also und i0 i blended or itated gently, .35 possess the same desirable equalities.

The nonreactive, phosphoric acid-asbestos composition The Proportions 0f the above described molding so produced may be rendered reactive by the application Position mixture are not efiiieai- The molding p of heat and pressure, or by pressure alone. In a hot moldtion mixture may contain from 20 to 70 percent by weight ing process, these dry compositions are thus activated of asbestos fibers and 30 to 80 percent by weight of dry, and made at least somewhat fiowable as they are molded 40 free-flowing acid containing powder. The powder may and these factors facilitate the use of the nonreactivecomcontain from to percent by weight of phosphoric p lp of e present lnventwn as extremely deslrable acid and 20 to 50 percent by weight of diatomaceous earth moldlng materials. material raiifii 213251552? Sfiffiiilfiiiiiifififi tili iifif ii r f W sitions of this invention were found to be g hy position taught in the present invention maybe best illusbetter than those of articles In 1d d f trated by reference to st1ll another example 1n WhlCh o e rom the prior art t grams of 75% aqueous phosphoric acid was blended with ype, short working life asbestos-phosphoric acid type 30 rams of C 1E t f d d compositions, such as that of the Brink et al. patent, for g i e O POW cry niate' examplfil 50 rial. Thls material was blended with 192 grams of mlxed As an illustration of the manufacture and use of the long i short fiber chrysome asbestos and Portions of molding composition of the present invention, the followthe mlxiure were molded at.300 and 4000 pounds per ing example is given: square inch pressure, at vanous intervals up to four days o h d grams of Mi 1 was mixed with after mixing. The fiexural strength, impact resistance rela- 400 grams f 75% aqueous phosphgfic acid, The acid tive to a common standard, and average hardness, at the was added in small portions t th Micr -CeLE l l middle and at the ends of the molded article both in the stirring the mix. The glass beaker containing the mix was direction of and perpendicular to the molding force cooled externally in tap water during the mixing operarection, may be seen in Table I for the molded articles tion which lasted approximately 5 minutes. The cooling produced at these various time intervals.

TABLE I Hardness-molding force Hardness-cross molding Flexural Impact irection force Time strength resistance (p.s.i.) (relative) v Middle Ends Middle Ends (average) (average) u (average) (average) 0 3, 568 4. 2-6. 2 55 54 54 50 -1 hour 4, 043 3.3 .6 53 54 54 51 3 hours 4, 409 5. 4-12. 0 56 55 55 56 4, 359 4. 1-11. 4 55 54 56 46 4, 30s 5. 7-10. 5 55 53 51 54 3, 766 5. 5-9. 5 51 52 5t; 50 3, 920 2. 1-3. 9 5s 51 33 25 Accordingly, the foregoing has shown that there has been provided a hot-molding composition, of the asbestosphosphoric acid type, having a very long storage life at room temperature. This is in contrast to the compositions of the prior art which require either extensive cooling or immediate use after mixing. In addition, improvements are noted in the crystalline structure of molded articles produced from compositions produced according to the present invention, and in the physical properties of these articles as compared to those produced by known methods. This may be seen, for example, in FIGURES 1 and 2, which are photomicrographs of the crystalline structure of hot-molded articles using the molding composition of the prior art and that of the present invention, respectively. FIGURE 1 shows the crystalline structure of a molded article produced from chrysotile asbestos and liquid aqueous phosphoric acid solution. The white masses in this figure are free asbestos fibers which can be seen throughout the structure. A general nonhomogeneous distribution of components is also apparent. This is in contrast to the crystalline structure, shown in FIGURE 2, of molded articles produced from the molding composition of the present invention. The crystalline structure of this article is characterized by homogeneity and practically a total absence of free asbestos fibers.

While the present invention has been described with reference to particular embodiments thereof, it will be understood that numerous modifications may be made by those skilled in the art without departing from the true spirit and scope of the invention. Therefore, the appended claims are intended to cover all such equivalent variations which come within the true spirit and scope of the present invention,

What is claimed as new and desired to be secured by Letters Patent of the United States is:

1. A method of preparing an inorganic thermosetting molding composition comprising:

(a) gently mixing from about 50 to 80 percent by weight of ortho-phosphoric acid and from about to 50 percent by weight of diatomaceous earth to provide a dry, free-flowing acid containing powder; and

(b) gently dry blending 20 to 70 percent by weight of chrysotile asbestos fibers with to 80 percent by weight of said dry, free-flowing acid containing powder.

2. A method of preparing an inorganic thermosetting molding composition comprising:

(a) gently mixing four parts by weight of orthophosphoric acid and one part by weight of a calcium silicate produced by a hydrothermal reaction of diatomaceous earth with an alkaline earth metal hydroxide to provide a dry, free-flowing acid containing powder; and

(b) gently dry blending 50 to 60 percent by weight of chrysotile asbestos fibers with to percent by weight of said dry free-flowing acid containing powder.

References Cited UNITED STATES-PATENTS 1,435,416 11/1922 Ottman 106-63 2,687,967 8/1954 Yedlick et a1. 1066 3 JAMES E. POER, Primary Examiner, 

